US20060154480A1 - Vaporizer for cvd, solution voporizing cvd system and voporization method for cvd - Google Patents
Vaporizer for cvd, solution voporizing cvd system and voporization method for cvd Download PDFInfo
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- US20060154480A1 US20060154480A1 US10/526,786 US52678605A US2006154480A1 US 20060154480 A1 US20060154480 A1 US 20060154480A1 US 52678605 A US52678605 A US 52678605A US 2006154480 A1 US2006154480 A1 US 2006154480A1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/14—Feed and outlet means for the gases; Modifying the flow of the reactive gases
Definitions
- the present invention relates to a vaporizer for CVD (Chemical Vapor Deposition), a solution-vaporization type CVD apparatus and a vaporization method for CVD.
- the present invention relates to a vaporizer for CVD, a vaporization method for CVD and a solution-vaporization type CVD apparatus including the vaporizer which can suppress a clogging at a solution pipe etc., for extending continuous operation times thereof.
- a ferroelectric thin film (thickness: 400-300 nm) formed by the solution coating process has poor step coverage. Moreover, when it is thinned (thickness: 150-40 nm), the number of pin holes are increased, whereby electrical isolation thereof is decreased. Because a FeRAM-LSI has a plurality of steps and requires the thinning of a ferroelectric material (thickness: 100-50 nm), it is necessary that a high-quality ferroelectric thin film be formed by CVD in order to attempt to put a FeRAM-LSI to practical use.
- Dr. Shiozaki an assistant professor in the engineering Dept. at Kyoto University, formed a ferroelectric thin film PZT by CVD and announced this formation at an academic conference.
- a CVD apparatus used by Dr. Shiozaki adopted a technique for vaporizing (gasifying) a solid chemical by sublimation.
- Sr(DPM) 2 , BiPh 3 , Ta(OEt) 5 , Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 , Bi(OtAm) 3 , Bi(MMP) 3 , etc. are used particularly, when Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 +Bi(MMP) 3 is used, a high-speed deposition (5-100 nm/min) at 320-420° C. can be performed, whereby a high-quality SBT thin film having good step coverage and electrical property can be formed.
- FIG. 11 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 .
- This figure illustrates: a graph 101 representing changes in a weight of a sample of Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 when the sample is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under argon atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.; a graph 102 representing changes in a weight of the sample when it is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min.
- FIG. 12 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of Bi(OtAm) 3 .
- This figure illustrates: a graph 111 representing changes in a weight of a sample of Bi(OtAm) 3 when the sample is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under argon atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.; a graph 112 representing changes in a weight of the sample when it is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min.
- FIG. 13 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of Bi(MMP) 3 .
- This figure illustrates: a graph 121 representing changes in a weight of a sample of Bi(MMP) 3 when the sample is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under argon atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.; a graph 122 representing changes in a weight of the sample when it is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min.
- FIG. 14 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of a mixture of Bi(OtAm) 3 /Sr[Ta(OEt) 6 ] 2 .
- This figure illustrates: a graph 131 representing changes in a weight of a sample of Bi(OtAm) 3 /Sr[Ta(OEt) 6 ] 2 when the sample is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under argon atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.; and a graph 133 representing changes in a weight of the sample when it is subject to a temperature rising from 30 to 600° C.
- NMR characteristic Nuclear Magnetic Resonance of H
- FIG. 16 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of a mixture of Bi(MMP) 3 /Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 .
- This figure illustrates a graph representing changes in a weight of a sample of Bi(MMP) 3 /Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 when the sample is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under argon atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.
- only 80% of the mixture of Bi(MMP) 3 /Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 sublimes under argon atmosphere.
- FIG. 17 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of BiPh 3 .
- This figure illustrates: a graph 141 representing changes in a weight of a sample of BiPh 3 when the sample is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under argon atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.; a graph 142 representing changes in a weight of the sample when it is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min.
- FIG. 18 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of BiPh 3 /Sr[Ta(OEt) 6 ] 2 .
- This figure illustrates: a graph 151 representing changes in a weight of a sample of BiPh 3 /Sr[Ta(OEt) 6 ] 2 when the sample is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under argon atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.; and a graph 153 representing changes in a weight of the sample when it is subject to a temperature rising from 30 to 600° C. at a rate of 10° C./min. under oxygen atmosphere at a pressure of 760 Torr and a flow rate of 100 ml/min.
- almost 100% of BiPh 3 /Sr[Ta(OEt) 6 ] 2 sublimes at approximately 280° C.
- FIG. 19 illustrates NMR characteristics representing stability of mixing BiPh 3 and Sr[Ta(OEt) 6 ] 2 . No synthesis of a new material is observed in a mixture of BiPh 3 /Sr[Ta(OEt) 6 ] 2 .
- FIG. 20 is a TG-DTA CHART (O 2 760 Torr) of BiPh 3 .
- an oxidation reaction of BiPh 3 occurs at 465° C.
- the oxidizing temperature of BiPh 3 is so high with respect to 259° C. of Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 , 209° C. of Bi(MMP) 3 , and 205° C. of Bi(OtAm) 3 , it is thus difficult to use BiPh 3 .
- Bi(OtAm) 3 causes a hydrolysis reaction with only 180 ppm of moisture. This means that Bi(OtAm) 3 is remarkably more sensitive to moisture than Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 causing a hydrolysis reaction with 1650 ppm of moisture, and Bi(MMP) 3 causing that reaction with 170 ppm of moisture, and thus the treatment of Bi(OtAm) 3 is difficult. Since moisture certainly exists, Bi(OtAm) 3 may be allowed to react with moisture to form Bi oxide, while a possibility that a pipe, a flow meter, etc. are clogged by the formed Bi oxide may increase.
- the present invention has been made to solve the above problems. It is, accordingly, an object of the present invention to provide a vaporizer for CVD, a solution-vaporization type CVD apparatus, and a vaporization method for CVD which can suppress a clogging at a solution pipe etc., so as to extend continuous operation times thereof.
- a vaporizer for CVD which comprises: a dispersing portion dispersing a plurality of raw-material solutions in a carrier gas in fine particulate or misty forms; a plurality of paths for the plurality of raw-material solutions, each of the plurality of paths supplying the plurality of raw-material solutions to the dispersing portion separately from one another; a path for the carrier gas, the path supplying the carrier gas to the dispersing portion separately from the plurality of raw-material solutions; a vaporizing member vaporizing the plurality of raw-material solutions dispersed by the dispersing portion; an orifice connected to the vaporizing member and the dispersing portion, the orifice introducing the plurality of raw-material solutions dispersed by the dispersing portion into the vaporizing member; and a cleaning mechanism cleaning at least one of the dispersing portion, the orifice and the vaporizing member.
- the dispersing portion since it has the cleaning mechanism, at least one of followings can be cleaned: the dispersing portion; the orifice; and the vaporizing member.
- the vaporization of the plurality of raw-material solutions are continuously carried out, solutes of the raw-material solutions gradually precipitate on at least one of the dispersing portion, the orifice and the vaporizing tube, and thus the orifice is gradually clogged.
- the clogging can be eliminated.
- the above described vaporizer may further comprise a monitoring mechanism for monitoring a pressure of the carrier gas. By observing the pressure thereof with the monitoring mechanism, the condition of the clogging of the orifice can be observed. Accordingly a proper timing for cleaning at least one of the dispersing portion, the orifice and the vaporizing tube can be determined.
- a vaporizer for CVD which comprises: a dispersing portion dispersing a plurality of raw-material solutions in a carrier gas in fine particulate or misty forms; a plurality of paths for the plurality of raw-material solutions, each of the plurality of paths supplying the plurality of raw-material solutions to the dispersing portion separately from one another; a path for the carrier gas, the path supplying the carrier gas to the dispersing portion separately from the plurality of raw-material solutions; a monitoring mechanism for monitoring a pressure of the carrier gas; a vaporizing member vaporizing the plurality of raw-material solutions dispersed by the dispersing portion; and an orifice connected to the vaporizing member and the dispersing portion, the orifice introducing the plurality of raw-material solutions dispersed by the dispersing portion into the vaporizing member.
- the dispersing portion be arranged in between the orifice and respective leading ends of the plurality of paths, and the orifice have a smaller diameter than those of the plurality of the paths and the path for the carrier gas.
- the vaporizing member be brought into a reduced pressure state and the dispersing portion be brought into an increased pressure state when the plurality of raw-material solutions vaporized.
- a vaporizer for CVD which comprises: a plurality of pipes for a plurality of raw-material solutions, each of the plurality of pipes supplying the plurality of raw-material solutions separately from one another; a pipe for a carrier gas, the pipe being provided in a manner covering outwards of the plurality of pipes, while the pipe allowing the pressurized carrier gas to flow thereinside and the outward of each of the plurality of pipes; an orifice provided on a leading end of the pipe for the carrier gas, the orifice being spaced away from leading ends of the plurality of pipes for the plurality of raw-material solutions; a vaporizing tube connected to the leading end of the pipe for the carrier gas, the vaporizing tube being connected to the inside of the pipe for the carrier gas via the orifice; a cleaning mechanism cleaning at least one the leading end of the pipe for the carrier gas, the orifice, the vaporizing tube and a heating means for heating the vapor
- the vaporizer since it has the cleaning mechanism, at least one of the followings can be cleaned: the leading end of the pipe for the carrier gas; the orifice; and the vaporizing tube.
- the vaporization of the plurality of raw-material solutions are continuously carried out, solutes of the raw-material solutions gradually precipitate on at least one of the leading end of the pipe for the carrier gas, the orifice and the vaporization tube, and thus the orifice is gradually clogged.
- the clogging can be eliminated.
- the above-described vaporizer may further comprise a monitoring mechanism for monitoring a pressure of the carrier gas in the inside of the pipe for the carrier gas. By observing the pressure thereof with the monitoring mechanism, the condition of the clogging of the orifice can be observed. Accordingly a proper timing for cleaning can be determined.
- the cleaning mechanism may clean the leading end of the pipe for the carrier gas and the orifice by supplying at least one solution thereto.
- the carrier gas and the plurality of raw-material solutions are mixed in between the orifice in the pipe for the carrier gas and respective leading ends of the plurality of pipes, the plurality of raw-material solutions are dispersed in the carrier gas in fine particulate or misty forms, the plurality of dispersed raw-material solutions in fine particulate or misty forms are introduced into the vaporizing tube via the orifice and heated by the heater so as to be vaporized.
- the orifice have a smaller diameter than those of the plurality of the pipes and the pipe for the carrier gas.
- the plurality of raw-material solutions can be one made by mixing Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 and a solvent, and one made by mixing Bi(MMP) 3 and a solvent, while the carrier gas can be argon or nitrogen gas.
- a solution-vaporization CVD apparatus which comprises one of the above-identified vaporizer for CVD.
- a solution-vaporization CVD apparatus which comprises at least one vaporizer for CVD above described, and a reaction chamber being connected to the vaporizer, wherein a deposition is carried out with the plurality of raw-material solutions used, the plurality of raw-material solutions being vaporized by the vaporizing tube.
- the above-described solution-vaporization CVD apparatus it may be equipped with the plurality of vaporizers for CVD; some of the plurality of vaporizers for CVD may be respectively in a cleaned condition cleaned by the cleaning mechanism, while others thereof may be respectively in operated condition; and the plurality of vaporized raw-material solutions may be continuously supplied to the reaction chamber by swapping the plurality of vaporizers for CVD in the operated conditions for those in the cleaned conditions as time advances.
- a vaporization method for CVD which comprises processes of: supplying a plurality of raw-material solutions and a carrier gas to a dispersing portion separately from one another; mixing the plurality of raw-material solutions and the carrier gas by the dispersing portion and dispersing the plurality of raw-material solutions in the carrier gas in fine particulate or misty forms; vaporizing the raw-material solutions by adiabatic expansion immediately after dispersing; and cleaning at least one of the dispersing portion and an area for vaporizing the raw-material solutions.
- a vaporization method for CVD which comprises processes of: supplying a plurality of raw-material solutions and a carrier gas to a dispersing portion separately from one another; mixing the plurality of raw-material solutions and the carrier gas by the dispersing portion, and dispersing the plurality of raw-material solutions in the carrier gas in fine particulate or misty forms; vaporizing the raw-material solutions by adiabatic expansion immediately after dispersing; observing a pressure of the carrier gas while vaporizing the raw-material solutions, and terminating the supply of the raw-material solutions to the dispersing portion upon observing that the pressure of the carrier gas exceeds a predetermined value; and cleaning at least one of the dispersing portion and an area for vaporizing the plurality of raw-material solutions.
- the process for cleaning may be one for cleaning at least one of the dispersing portion and the area for vaporizing the plurality of raw-material solutions by supplying a solvent and the carrier gas thereto; and the pressure of the carrier gas may be monitored during the process for cleaning so that the supply of the solvent is terminated upon observing that the pressure of the carrier gas is turned less than or equal to the predetermined value so as to terminate the process for cleaning.
- the solvent for cleaning and solvents contained in the plurality of raw-material solutions may be homogeneous.
- the solvent for cleaning may be one or a mixture of those selected from a group consisting of ethyl cyclohexane, n-hexane, benzene, toluene, octane, or decane.
- a vaporizer for CVD a solution-vaporization CVD apparatus, and a vaporization method for CVD which can suppress a clogging at a solution-pipe etc., so as to extend continuous operation times thereof.
- FIG. 1A is a schematic view illustrating a structure of a solution supplying system included in a vaporizer for CVD according to a first embodiment of the present, invention
- FIG. 1B is a schematic cross sectional view illustrating the solution supplying system of the vaporizer, a dispersing portion thereof, and a vaporizing member thereof;
- FIG. 2C is a schematic view illustrating a structure of a solution supplying system included in a vaporizer for CVD according to a second embodiment of the present invention
- FIG. 2D is a schematic view illustrating a structure of a solution supplying system included in a vaporizer for CVD according to a third embodiment of the present invention
- FIG. 3 is a view illustrating an experimental result that pressures of a carrier gas were monitored
- FIG. 4 is a view illustrating an experimental result that pressures of a carrier gas were monitored
- FIG. 5 is a view illustrating an experimental result that pressures of a carrier gas were monitored
- FIG. 6 is a view illustrating an experimental result that pressures of a carrier gas were monitored
- FIG. 7 is a view illustrating an experimental result that pressures of a carrier gas were monitored
- FIG. 8 is a view illustrating an experimental result that pressures of a carrier gas were monitored
- FIG. 9 is a view illustrating a result of an experiment of reproducibility of SBT-CVD with the vaporizer according to the first embodiment
- FIG. 10 is a view illustrating the result of the experiment of reproducibility of SBT-CVD with the vaporizer according to the first embodiment
- FIG. 11 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 ;
- FIG. 12 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of Bi(OtAm) 3 ;
- FIG. 13 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of Bi(MMP) 3 ;
- FIG. 14 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of a mixture of Bi(OtAm) 3 /Sr[Ta(OEt) 6 ] 2 ;
- FIG. 15 a view illustrating NMR characteristic (nuclear magnetic resonance of H).
- FIG. 16 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of a mixture of Bi(MMP) 3 /Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 ;
- FIG. 17 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of BiPh 3 ;
- FIG. 18 is a TG CHART (Ar 760/10 Torr, O 2 760 Toor) of BiPh 3 /Sr[Ta(OEt) 6 ] 2 ;
- FIG. 19 is a view illustrating NMR characteristics representing stability of mixing BiPh 3 and Sr[Ta(OEt) 6 ] 2 ;
- FIG. 20 is TG-DTA CHART (O 2 760 Torr) of BiPh 3 .
- FIG. 1A is a schematic view illustrating a structure of a solution supplying system included in a vaporizer for CVD according to a first embodiment of the present invention
- FIG. 1B is a schematic cross sectional view illustrating the solution supplying system of the vaporizer, a dispersing portion thereof, and a vaporizing member thereof.
- the vaporizer for CVD has first and second pipes 1 , 2 for raw-material solutions.
- the first pipe 1 is provided adjacent to the second pipe 2 in parallel therewith.
- a pipe 3 for a carrier gas is provided outwardly relative to the first and second pipes 1 , 2 .
- An internal diameter of the pipe 3 is formed to be larger than a sum of an external diameter of the first pipe 1 and that of the second pipe 2 .
- the first and second pipes 1 , 2 are inserted into the inside of the pipe 3 , while the pipe 3 is formed in a manner containing the first and second pipes 1 , 2 thereinside.
- a base end of the first pipe 1 is connected to a first supplying mechanism 4 for supplying a chemical 1 and a solvent.
- the first supplying mechanism 4 has a chemical-supplying-source for supplying the chemical 1 (for instance, Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 ), and a solvent-supplying-source for supplying the solvent.
- a valve 6 and a mass-flow controller are provided in between the chemical-supplying-source and the first pipe 1 .
- a valve 7 and a mass-flow controller are provided in between the solvent-supplying-source and the first pipe 1 . The solvent and the chemical 1 flow into each other (mix) in between the solvent-supplying-source and the first pipe 1 .
- a base end of the second pipe 2 is connected to a second supplying mechanism 5 for supplying a chemical 2 and a solvent.
- the second supplying mechanism 5 has a chemical-supplying-source for supplying the chemical 2 (for instance, Bi(MMP) 3 ), and a solvent-supplying-source for supplying the solvent.
- a valve 8 and a mass-flow controller are provided in between the chemical-supplying-source and the second pipe 2 .
- a valve 9 and a mass-flow controller are provided in between the solvent-supplying-source and the second pipe 2 .
- the solvent and the chemical 2 flow into each other (mix) in between the solvent-supplying-source and the second pipe 2 .
- a base end of the pipe 3 is connected to a third supplying mechanism 12 for supplying an argon gas and a nitrogen gas.
- the third supplying mechanism 12 has an argon-gas-supplying-source for supplying the argon gas (Ar), and a nitrogen-gas-supplying-source for supplying the nitrogen-gas (N 2 ).
- a valve 10 and a mass-flow controller are provided in between the argon-gas-supplying-source and the pipe 3 .
- a valve 11 and a mass-flow controller are provided in between the nitrogen-gas-supplying-source and the pipe 3 .
- a high-precision pressure gauge 17 is provided in between the third supplying mechanism 12 and the pipe 3 , while the high-precision pressure gauge 17 is one for constantly monitoring a pressure of the carrier gas in the inside of the pipe 3 .
- the high-precision pressure gauge 17 sends an output signal to a non-illustrated controller. Based on the output signal, the pressure of the carrier gas can be displayed by a non-illustrated control-monitor and monitored.
- a leading end of the pipe 3 is connected to one end of a vaporizing tube 13 .
- An orifice is formed on the leading end of the pipe 3 , while it allows the inside of the pipe 3 and that of the vaporizing tube 13 to be connected with each other.
- a heater is provided around the vaporizing tube 13 , while the vaporizing tube 13 is heated at, for instance, 270° C. by the heater.
- the other end of the vaporizing tube 13 is connected to a non-illustrated reaction chamber.
- a dispersing portion 14 is formed in between the respective leading ends of the first and second pipes 1 , 2 in the inside of the pipe 3 and the orifice.
- the dispersing portion 14 mixes: a first raw-material solution (one made by mixing the chemical 1 and the solvent thereof) flows out of the leading end of the first pipe 1 ; a second raw-material solution (one made by mixing the chemical 2 and the solvent thereof) flows out of the leading end of the second pipe 2 ; and the argon or nitrogen gas flows out of the pipe 3 , and then disperses the first and second raw-material solutions in the argon or nitrogen gas in fine particulate or misty forms.
- the valve 6 is opened so as to supply the first raw-material solution from the first supplying mechanism 4 to the first pipe 1 at predetermined flow rate and pressure.
- the first raw-material solution is, for instance, one made by mixing Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 and the solvent thereof.
- the valve 8 is opened so as to supply the second raw-material solution from the second supplying mechanism 5 to the second pipe 2 at predetermined flow rate and pressure.
- the second raw-material solution is, for instance, one made by mixing Bi(MMP) 3 and the solvent thereof.
- the valves 10 , 11 are opened so as to supply the carrier gas from the third supplying mechanism 12 to the pipe 3 at predetermined flow rate and pressure.
- the carrier gas is, for instance, the argon or nitrogen gas.
- the first raw-material solution is supplied to the dispersing portion 14 via the first pipe 1
- the second raw-material solution is also supplied to the dispersing portion 14 via the second pipe 2
- the pressurized carrier gas is supplied to the dispersing portion 14 via the pipe 3 .
- the dispersing portion 14 mixes the first raw-material solution, the second raw-material solution and the carrier gas, while it disperses the first and second raw-material solutions in the carrier gas in fine particulate or misty forms. It is preferable that the first and second raw-material solutions mixed by the dispersing portion 14 be dispersed in fine particulate or misty forms within a single second.
- the first and second raw-material solutions dispersed in the carrier gas by the dispersing portion 14 are introduced into the vaporizing tube 13 via the orifice.
- the first and second raw-material solutions dispersed in misty forms are instantaneously heated at approximately 270° C. by the heater.
- the inside of the vaporizing portion 13 is in a reduced pressure condition, while the dispersing portion 14 is in an increased pressure condition.
- the pressure of the inside of the vaporizing portion 13 is, for instance, 5-30 Torr, while that of the inside of the dispersing portion 14 is, for instance, 1500-2200 Torr.
- the raw-material solutions (with the chemicals) can be vaporized by the heat from the heater.
- the first and second raw-material solutions are turned to be fine mist by the high-speed flow of the carrier gas immediately after dispersed by the dispersing portion 14 , and thus they are easily vaporized instantaneously.
- a source gas is produced by vaporizing the first and second raw-material solutions in the vaporizer for CVD.
- the source gas is introduced into a reaction chamber via the vaporizing tube 13 , while a thin film is deposited on a substrate to be processed by CVD.
- the pressure of the carrier gas is constantly monitored by the high-precision pressure gauge 17 .
- solutes of the raw-material solutions gradually precipitate on at least one of the dispersing portion 14 and the orifice, and thus the orifice (atomizing nozzle) is gradually clogged. The phenomenon is as follow.
- the controller is notified by the high-precision pressure gauge 17 that the pressure of the carrier gas exceeds the predetermined value (for instance, 200 KPa) by receiving an output signal therefrom, the valves 6 , 8 are closed so as to terminate the supply of the solutions of Sr[TA(OEt) 5 (OC 2 H 4 OMe)] 2 and Bi(MMP) 3 , while the valves 7 , 9 are opened so as to allow only the solvents to flow.
- an outlet of the vaporizing tube 13 is changed from a reactor to an exhaust portion (not illustrated), the solutions and the carrier gas are only supplied to the pipes 1 to 3 for cleaning.
- the atomizing nozzle sprays the solvents, while the solutes precipitating thereon are re-dissolved by the solvents, whereby they are eliminated therefrom.
- the solvents for the cleaning are supplied from the first and second supplying mechanisms, but the supply thereof is not limited to this.
- a solvent supplying mechanism for the cleaning may be separately provided, while a solvent for the cleaning may be supplied from this solvent supplying mechanism.
- the substrate to be processed be taken out from the reaction chamber prior to the cleaning, while a new substrate to be processed be put into the reaction chamber after the cleaning.
- the cleaning be carried out prior to the detection of the clogging. For instance, the reproducibility can be improved by cleaning the vaporizing tube 13 or the like during a period of a waiting time with a couple of minutes between one substrate is processed and the next CVD-thin-film-deposition process is performed with the next substrate being put into the reaction chamber.
- the pressure of the carrier gas in the pipe 3 is also monitored by the high-precision pressure gauge 17 . Accordingly, a condition of the clogging of the orifice can be monitored. As the cleaning process continued, the clogging of the orifice (atomizing nozzle) can be gradually eliminated since the precipitated solutes are dissolved. Accordingly, the pressure of the carrier gas is lowered. After the controller is notified by the high-precision pressure gauge 17 that the pressure of the carrier gas is turned less than or equal to the predetermined value (for instance, 100 KPa) by receiving an output signal therefrom, the valves 6 , 8 are re-opened so as to re-supply the raw-material solution.
- the predetermined value for instance, 100 KPa
- the capacities of the pipes from the valves 6 to 9 to the leading edges of the pipes 1 , 2 be less than or equal to 8 Xcc, more preferably, less than or equal to 2 Xcc, and further preferably, less than or equal to Xcc.
- the timing for the cleaning in order to eliminate the clogging of the atomizing nozzle with the solutions is determined by the high-precision pressure gauge 17 monitoring the pressure of the carrier gas, but not limited to this.
- the cleaning may be carried out by allowing the solutions and carrier gas to flow after predetermined times pass.
- the orifice atomizing nozzle
- the vaporizer for CVD can be used for a significantly long time by performing the cleaning process during the operation thereof. It takes approximately 10 hours for disassembling the clogged vaporizer, cleaning and reassembling it.
- the above-described cleaning process can be finished within a couple of minutes, and thus the operation time of the vaporizer can be considerably extended, while a production cost for a semiconductor device or the like can be considerably reduced.
- the first and second pipes 1 , 2 are provided adjacent to each other and in parallel with each other, while the pipe 3 for the carrier gas is provided outwardly relative to the first and second pipes 1 , 2 . Accordingly, the first raw-material solution (Sr[Ta(OEt) 5 (OEtOMe)] 2 ) and the second raw-material solution (Bi(MMP) 3 can be separately supplied to the dispersing portion 14 , whereby a chemical reaction of the first and second solutions in solution states does not occur, while the clogging in the inside of the pipe can be prevented. Therefore, the continuous operation time of the vaporizer for CVD can be extended.
- the first and second pipes 1 , 2 are contained in the pipe 3 having a larger diameter, the carrier gas is allowed to flow a space in between the first, second pipes 1 , 2 and the pipe 3 , while the vaporizing tube 13 is provided on a downstream side of the flow. Since the pressurized carrier gas is allowed to flow the space locating the outsides of the pipes 1 , 2 at a high speed, a temperature rise in the first, second pipes 1 , 2 , the pipe 3 and the dispersing portion 14 can be suppressed.
- the dispersing portion 14 a chemical reaction caused by the raw-material solutions can be suppressed since it is suppressed that only the solvents of the raw-material solutions vaporize, and thus the clogging of the dispersing portion 14 or the orifice can be suppressed. Therefore, the continuous operation time of the vaporizer for CVD can be extended.
- the first and second raw-material solutions are dispersed in fine particulate or misty forms immediately after mixed with the carrier gas by the dispersing portion 14 (within a single second). It is thus suppressed that only the solvents of the raw-material solutions vaporize. Accordingly, in the dispersing portion 14 , a chemical reaction of the raw-material solutions by the dispersing portion 14 can be suppressed, and thus the clogging of the dispersing portion 14 or the orifice can be suppressed. Therefore, the continuous operation time of the vaporizer for CVD can be extended.
- the first and second raw-material solutions are dispersed by the dispersing portion 14 , while the dispersed raw-material solutions in fine particulate or misty forms are heated in the inside of the vaporizing tube 13 so as to be vaporized (gasified) instantaneously. It is thus suppressed that only the solvent of the raw-material solutions vaporizes. Accordingly, in the orifice or the vaporizing tube 13 adjacent to the orifice, a chemical reaction of the raw-material solutions can be suppressed, and thus the clogging of the orifice or the vaporizing tube 13 can be suppressed. Therefore, the continuous operation time of the vaporizer for CVD can be extended.
- the clogging of the pipes 1 to 3 , the dispersing portion 14 , the orifice and the vaporizing tube 13 can be prevented, and even if they are clogged, the cleaning is carried out for bringing them into the original conditions. Accordingly, the vaporizer for CVD can be continuously operated for long time. Therefore, a thin film of a ferroelectric material such as PZT, SBT or the like can be deposited with good reproducibility and controllability, while the vaporizer and the solution-vaporization CVD of high performance can be embodied.
- a ferroelectric material such as PZT, SBT or the like
- a solution-vaporization CVD apparatus which can continuously deposit over several hundred hours can be embodied.
- a reaction chamber is equipped with 12 vaporizers each having the cleaning mechanism, and during the operation of the solution-vaporization CVD apparatus, two vaporizers among them are cleaned, while other 10 vaporizers are continuously operated.
- the solution-vaporization CVD apparatus which sequentially cleans at least one of the vaporizers so as to carry out a continuous deposition, is suitable for a case that, for instance, YBCO of a superconductive oxide thin film with a thickness of 10 ⁇ m is formed on a substrate having an extremely long tape shape.
- FIG. 2C is a schematic view illustrating a structure of a solution supplying system included in a vaporizer for CVD according to a second embodiment of the present invention.
- the same structure portions as those illustrated in FIG. 1A will be denoted the same reference numbers, respectively, while detailed explanations thereof will be omitted.
- the vaporizer for CVD illustrated in FIG. 2C has three pipes 1 , 2 and 15 for supplying three kinds of raw-material solutions, respectively.
- the first pipe 1 , the second pipe 2 and the third pipe 15 are provided adjacent to one another and in parallel with one another.
- the pipe 3 for a carrier gas is provided outwardly relative to the first to third pipes 1 , 2 and 15 .
- the first to third pipes 1 , 2 and 15 are inserted into the inside of the pipe 3 , while the pipe 3 is formed in a manner containing the first to third pipes 1 , 2 and 15 thereinside.
- a base end of the third pipe 15 is connected to a third supplying mechanism (not illustrated) for supplying a chemical 3 and a solvent.
- the third supplying mechanism has a chemical-supplying-source for supplying the chemical 3 , and a solvent-supplying-source for supplying the solvent.
- a valve (not illustrated) and a mass-flow controller (not illustrated) are provided in between the chemical-supplying-source and the third pipe 15 .
- a valve (not illustrated) and a mass-flow controller (not illustrated) are provided in between the solvent-supplying-source and the third pipe 15 .
- the solvent and the chemical 3 flow into each other (mix) in between the solvent-supplying-source and the third pipe 15 .
- Leading ends of the first to third pipes 1 , 2 and 15 are spaced away from the orifice, respectively.
- a dispersing portion is formed in between the respective leading ends of the first to third pipes 1 , 2 and 15 in the inside of the pipe 3 and the orifice.
- the dispersing portion mixes: a first raw-material solution (one made by mixing the chemical 1 and the solvent thereof) flows out of the leading end of the first pipe 1 ; a second raw-material solution (one made by mixing the chemical 2 and the solvent thereof) flows out of the leading end of the second pipe 2 ; a third raw-material solution (one made by mixing the chemical 3 and the solvent thereof) flows out of the leading end of the third pipe 15 ; and the argon or nitrogen gas flows out of the pipe 3 , and then disperses the first to third raw-material solutions into the argon or nitrogen gas in fine particulate or misty forms.
- FIG. 2D is a schematic view illustrating a structure of a solution supplying system included in a vaporizer for CVD according to a third embodiment of the present invention.
- the same structure portions as those illustrated in FIG. 2C will be denoted the same reference numbers, respectively, while detailed explanations thereof will be omitted.
- the vaporizer for CVD illustrated in FIG. 2D has four pipes 1 , 2 , 15 and 16 for supplying four kinds of raw-material solutions.
- the first pipe 1 , the second pipe 2 , the third pipe 15 and the fourth pipe 16 are provided adjacent to one another and in parallel with one another.
- the pipe 3 for a carrier gas is provided outwardly relative to the first to fourth pipes 1 , 2 , 15 and 16 .
- the first to fourth pipes 1 , 2 , 15 and 16 are inserted into the inside of the pipe 3 , while the pipe 3 is formed in a manner containing the first to fourth pipes 1 , 2 , 15 and 16 thereinside.
- a base end of the fourth pipe 16 is connected to a fourth supplying mechanism (not illustrated) for supplying a chemical 4 and a solvent.
- the fourth supplying mechanism has a chemical-supplying-source for supplying the chemical 4 , and a solvent-supplying-source for supplying the solvent.
- a valve (not illustrated) and a mass-flow controller (not illustrated) are provided in between the chemical-supplying-source and the fourth pipe 16 .
- a valve (not illustrated) and a mass-flow controller (not illustrated) are provided in between the solvent-supplying-source and the fourth pipe 16 .
- the solvent and the chemical 4 flow into each other (mix) in between the solvent-supplying-source and the fourth pipe 16 .
- Leading ends of the first to fourth pipes 1 , 2 , 15 and 16 are spaced away from the orifice, respectively.
- a dispersing portion is formed in between the respective leading ends of the first to fourth pipes 1 , 2 , 15 and 16 in the inside of the pipe 3 and the orifice.
- the dispersing portion mixes: a first raw-material solution (one made by mixing the chemical 1 and the solvent thereof) flows out of the leading end of the first pipe 1 ; a second raw-material solution (one made by mixing the chemical 2 and the solvent thereof) flows out of the leading end of the second pipe 2 ; a third raw-material solution (one made by mixing the chemical 3 and the solvent thereof) flows out of the leading end of the third pipe 15 ; a fourth raw-material solution (one made by mixing the chemical 4 and the solvent thereof) flows out of the leading end of the fourth pipe 16 ; and the argon or nitrogen gas flows out of the pipe 3 , and then disperses the first to fourth raw-material solutions in the argon or nitrogen gas in fine particulate or misty forms.
- the vaporizer, the vaporization method for CVD and the CVD apparatus according to the present invention can be applied variously, not only they are applied to the formation of a high-quality ferroelectric thin film (for instance, SBT, PZT) for a FeRAM-LSI as a ferroelectric memory, but also the formation of other films such as YBCO (super conductive oxide), thick PZT/PLZT/SBT film(for filter, MEMS, optical interconnect, HD), metal film (Ir, Pt, Cu), barrier metal (TiN, TaN), high k film(HfOx, Al 2 O 3 , BST or the like) with various kinds of chemicals used, for instance, a material having low vapor pressure.
- a high-quality ferroelectric thin film for instance, SBT, PZT
- a FeRAM-LSI ferroelectric memory
- other films such as YBCO (super conductive oxide), thick PZT/PLZT/SBT film(for filter, MEMS, optical interconnect,
- the first raw-material solution is made by dissolving Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 in the solution thereof, while the second raw-material solution is made by dissolving Bi(MMP) 3 in the solution thereof, but the raw-material solution is not limited to those.
- a raw-material solution may be made by dissolving the other kind of a solid material in a solution thereof.
- a liquid material of Sr[Ta(OEt) 5 (OC 2 H 4 OMe)] 2 or the like itself may be used as a raw-material solution, while one made by mixing a liquid material with a solution may be used.
- one kind of a thin film is formed on a substrate to be processed, respectively.
- plural kinds of thin films may be successively formed on a substrate.
- a raw-material solution and a carrier gas are allowed to flow into the reaction chamber (CVD chamber) via the vaporizing tube for CVD for an appropriate period so as to form a first thin film on a substrate.
- a valve for the raw-material solution is changed to be as an exhaust, while another kind of raw-material solution is supplied to the reaction chamber via the vaporizing tube at a predetermined flow rate.
- this raw-material solution that is, volume thereof
- this raw-material solution and a carrier gas are allowed to flow into the reaction chamber via the vaporizing tube for an appropriate period so as to form a second thin film on the substrate. Accordingly, two kinds of thin films having different compositions can be successively formed. Moreover, by repeating this process, three or more kinds of thin films can be formed. Meanwhile, when supplying another kind of raw-material solution to the reaction chamber, a temperature of the substrate and a pressure when reacting may be appropriately changed.
- FIGS. 3 to 8 Resultants of monitoring the pressures of the carrier gas are illustrated in FIGS. 3 to 8 .
- the pressure of the carrier gas gradually increased.
- the pressure of the BiMMP carrier gas reached to 220 kPa (approximately 2.2 barometric pressure (gage pressure)).
- the supply of BiMMP 0.2 ccm
- a cleaning solvent ECH 0.5 ccm
- the pressure of the carrier gas rapidly fell and stabilized at a monitor point 440 .
- FIGS. 9 and 10 illustrate resultants of a reproducibility experiment of SBT-CVD with the vaporizer of the present invention used.
- FIG. 9 illustrates reproducibility of deposition rate.
- FIG. 10 illustrates reproducibility of film composition.
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Applications Claiming Priority (3)
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JP2003432600 | 2003-12-26 | ||
JP2003-432600 | 2003-12-26 | ||
PCT/JP2004/006635 WO2005067017A1 (ja) | 2003-12-26 | 2004-05-17 | Cvd用気化器、溶液気化式cvd装置及びcvd用気化方法 |
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US20060154480A1 true US20060154480A1 (en) | 2006-07-13 |
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US10/526,786 Abandoned US20060154480A1 (en) | 2003-12-26 | 2004-05-17 | Vaporizer for cvd, solution voporizing cvd system and voporization method for cvd |
Country Status (6)
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US (1) | US20060154480A1 (zh) |
JP (1) | JP4019430B2 (zh) |
KR (1) | KR100693396B1 (zh) |
CN (1) | CN100411102C (zh) |
TW (1) | TW200524046A (zh) |
WO (1) | WO2005067017A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070120275A1 (en) * | 2005-11-28 | 2007-05-31 | Msp Corporation | High stability and high capacity precursor vapor generation for thin film deposition |
US20090074056A1 (en) * | 2003-12-23 | 2009-03-19 | International Business Machines Corporation | System for Preparing a Multimedia Stream |
US20090107402A1 (en) * | 2007-10-31 | 2009-04-30 | Samsung Electronics Co., Ltd. | Deposition apparatus and cleaning method thereof |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102017084B (zh) * | 2008-04-30 | 2012-09-05 | 株式会社菲尔科技 | 加热装置、膜形成装置及膜形成方法和元件 |
JP6008682B2 (ja) * | 2012-10-05 | 2016-10-19 | 大陽日酸株式会社 | 気相成長装置用配管のクリーニング方法 |
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US6098964A (en) * | 1997-09-12 | 2000-08-08 | Applied Materials, Inc. | Method and apparatus for monitoring the condition of a vaporizer for generating liquid chemical vapor |
US6258171B1 (en) * | 1998-07-23 | 2001-07-10 | Micron Technology, Inc. | Direct liquid injection system with on-line cleaning |
US20020192375A1 (en) * | 1997-06-02 | 2002-12-19 | Sun James J. | Method and apparatus for vapor generation and film deposition |
US6540840B1 (en) * | 1999-01-22 | 2003-04-01 | Kabushiki Kaisha Watanabe Shoko | Vaporizer for MOCVD and method of vaporizing raw material solutions for MOCVD |
Family Cites Families (5)
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JP2000026974A (ja) * | 1998-07-08 | 2000-01-25 | Fujitsu Ltd | 薄膜形成方法及び薄膜形成装置 |
US6500487B1 (en) * | 1999-10-18 | 2002-12-31 | Advanced Technology Materials, Inc | Abatement of effluent from chemical vapor deposition processes using ligand exchange resistant metal-organic precursor solutions |
JP2003273030A (ja) * | 2002-03-18 | 2003-09-26 | Watanabe Shoko:Kk | Cvd薄膜堆積の方法 |
JP2003309114A (ja) * | 2002-04-17 | 2003-10-31 | Japan Pionics Co Ltd | 気化供給方法及び気化供給装置 |
JP2003318170A (ja) * | 2002-04-26 | 2003-11-07 | Japan Pionics Co Ltd | 気化器 |
-
2004
- 2004-05-17 JP JP2005516786A patent/JP4019430B2/ja not_active Expired - Lifetime
- 2004-05-17 KR KR1020057003645A patent/KR100693396B1/ko not_active IP Right Cessation
- 2004-05-17 WO PCT/JP2004/006635 patent/WO2005067017A1/ja active Application Filing
- 2004-05-17 CN CNB2004800007630A patent/CN100411102C/zh not_active Expired - Fee Related
- 2004-05-17 US US10/526,786 patent/US20060154480A1/en not_active Abandoned
- 2004-12-24 TW TW093140494A patent/TW200524046A/zh not_active IP Right Cessation
Patent Citations (4)
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US20020192375A1 (en) * | 1997-06-02 | 2002-12-19 | Sun James J. | Method and apparatus for vapor generation and film deposition |
US6098964A (en) * | 1997-09-12 | 2000-08-08 | Applied Materials, Inc. | Method and apparatus for monitoring the condition of a vaporizer for generating liquid chemical vapor |
US6258171B1 (en) * | 1998-07-23 | 2001-07-10 | Micron Technology, Inc. | Direct liquid injection system with on-line cleaning |
US6540840B1 (en) * | 1999-01-22 | 2003-04-01 | Kabushiki Kaisha Watanabe Shoko | Vaporizer for MOCVD and method of vaporizing raw material solutions for MOCVD |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20090074056A1 (en) * | 2003-12-23 | 2009-03-19 | International Business Machines Corporation | System for Preparing a Multimedia Stream |
US20070120275A1 (en) * | 2005-11-28 | 2007-05-31 | Msp Corporation | High stability and high capacity precursor vapor generation for thin film deposition |
US8603580B2 (en) * | 2005-11-28 | 2013-12-10 | Msp Corporation | High stability and high capacity precursor vapor generation for thin film deposition |
US20090107402A1 (en) * | 2007-10-31 | 2009-04-30 | Samsung Electronics Co., Ltd. | Deposition apparatus and cleaning method thereof |
Also Published As
Publication number | Publication date |
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TW200524046A (en) | 2005-07-16 |
WO2005067017A1 (ja) | 2005-07-21 |
JP4019430B2 (ja) | 2007-12-12 |
CN100411102C (zh) | 2008-08-13 |
CN1717782A (zh) | 2006-01-04 |
KR100693396B1 (ko) | 2007-03-12 |
KR20060035570A (ko) | 2006-04-26 |
TWI305381B (zh) | 2009-01-11 |
JPWO2005067017A1 (ja) | 2007-07-26 |
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